The invention relates to the synthesis of polybenzoxazole (PBO), polybenzimidazole (PBI) or polybenzothiazole (PBT) and related polymers (hereinafter referred to as PBZ polymers).
PBZ polymers are a known class of polymers which contain a plurality of mer units comprising at least:
(1) a first aromatic group (Ar.sup.1); and PA0 (2) a first azole ring which is fused with the first aromatic group. PA0 (3) a second azole ring which is fused with the first aromatic group, and PA0 (4) a divalent group (DL), which is inert with respect to all reagents for making PBZ polymers under polymerization conditions, bonded by a single bond to the 2-carbon of the second azole ring. PA0 DL is a divalent group as previously described; and PA0 each Z is independently chosen from the group consisting of --O--, --S-- or --NR--, wherein R is an aliphatic or aromatic group which does not interfere with polymerization. PA0 (1) a first aromatic group (Ar.sup.1); PA0 (2) a first o-amino-basic moiety bonded to said first aromatic group, which o-amino-basic moiety contains: PA0 (a) a primary amine group bonded to the first aromatic group; and PA0 (3) an azole-forming group bonded to the first aromatic group which is either a second o-amino-basic group or an "electron-deficient carbon group," PA0 (1) a divalent group which is inert with respect to all reagents under reaction conditions; PA0 (2) an "electron-deficient carbon group," such as a carboxylic acid or acid salt; and PA0 (3) an azole-forming group which may be a second "electron-deficient carbon group" or, if the divalent group comprises an aromatic group, an o-amino-basic group. PA0 each Z is an oxygen atom, a sulfur atom or --NR--, wherein R is an aliphatic or aromatic group which does not interfere with polymerization and each Z is bonded to the first aromatic group (Ar.sup.1) ortho to a primary amine group (in the monomer) or the nitrogen atom of the azole ring in which it is located (in the polymer); PA0 DL is a divalent group as previously described; and PA0 each Q is an electron-deficient carbon group as previously described. PA0 (1) an azole-containing compound having: PA0 (2) a displacing compound having: PA0 (1) an organic moiety which is inert with respect to all reagents under reaction conditions; and PA0 (2) two reactive groups selected, such that a polymer is formed, from the class consisting of: PA0 (b) displacing groups having: a nucleophilic moiety, which is an oxygen atom, a sulfur atom or a nitrogen atom, bonded to said organic moiety; and a counter-moiety bonded to said nucleophilic moiety, PA0 (1) a first aromatic group; PA0 (2) an azole ring fused to said first aromatic group; PA0 (3) a second aromatic group bonded to the 2-carbon of said azole ring; PA0 (4) a leaving group bonded to said second aromatic group in a position where it is activated by said azole ring; PA0 (5) a nucleophilic moiety, as previously defined, linked to said first aromatic group in a position not ortho to the 4- or 5-carbon of the azole ring; and PA0 (6) a counter-moiety, as previously defined, bonded to said nucleophilic moiety. PA0 (1) an unfused first aromatic group (Ar.sup.1), which comprises two aromatic moieties (Ar.sup.1a and Ar.sup.1b) linked by a bond or a divalent linking moiety (D) which is inert with respect to nucleophilic aromatic substitution; PA0 (2) a first azole ring fused with one aromatic moiety (Ar.sup.1a) of said unfused first aromatic group, and a second azole ring fused with the other aromatic moiety (Ar.sup.1b) of said unfused first aromatic group; PA0 (3) a second aromatic group (Ar.sup.2) bonded to the 2-carbon of said first azole ring and a third aromatic group (Ar.sup.3) bonded to the 2-carbon of said second azole ring; and PA0 (4) a first leaving group bonded to said second aromatic group and a second leaving group bonded to said third aromatic group. PA0 (1) a first aromatic group; PA0 (2) an azole ring fused to said first aromatic group; PA0 (3) a second aromatic group bonded to the 2-carbon of said azole ring; and PA0 (4) an oxygen, sulfur or nitrogen atom linked to said first aromatic group and bonded by a single bond to a second aromatic group of an adjacent unit. PA0 (1) a first aromatic group; PA0 (2) an azole ring fused to said first aromatic group; PA0 (3) a second aromatic group bonded to the 2-carbon of said azole ring; and PA0 (4) an oxygen, sulfur or nitrogen atom linked to said first aromatic group and bonded by a single bond to a second aromatic group of an adjacent unit. PA0 (1) a first primary amine group bonded to the aromatic group and PA0 (2) a hydroxy, thiol or secondary amine group bonded to the aromatic group ortho to said primary amine group. PA0 (1) an azole ring; PA0 (2) an aromatic group bonded to the 2-carbon of said azole ring; and PA0 (3) a leaving group bonded to said aromatic group in a position such that it is activated by said azole ring. PA0 Ar* is an aromatic group of the azolecontaining compound, as previously defined; PA0 Z is as previously defined in describing the azole rings, PA0 L is a leaving group as previously described; PA0 Nu is --O--, --S--, or --NR-- as previously described in describing the nucleophilic moiety; and PA0 Y is a counter-moiety for the nucleophilic moiety as previously described. PA0 (1) an azole ring, as previously defined, bonded to the organic moiety; PA0 (2) an aromatic group, as previously defined, bonded to the 2-carbon of the azole ring; and PA0 (3) a leaving group, as previously defined, bonded to the aromatic group in a position where it is activated by the azole ring. PA0 (1) a nucleophilic moiety, as previously described, bonded to the organic moiety; and PA0 (2) a counter-moiety, as previously described, bonded to the nucleophilic moiety. PA0 (1) a first aromatic group; PA0 (2) an azole ring fused to said first aromatic group; PA0 (3) a second aromatic group bonded to the 2-carbon of said azole ring; PA0 (4) a leaving group bonded to said second aromatic group in a position where it is activated by said azole ring; PA0 (5) a nucleophilic moiety, as previously defined, linked to said first aromatic group in a position not ortho to the 4- or 5-carbon of said azole ring; and PA0 (6) a counter-moiety, as previously defined, bonded to said nucleophilic moiety. PA0 (1) an aromatic group corresponding to the first aromatic group of the monomer (Ar.sup.1); PA0 (2) an o-amino-basic moiety, as that moiety is previously described, bonded to said aromatic group, and PA0 (3) a nucleophilic moiety linked to said aromatic group (Ar.sup.1) and bonded to a hydrogen atom with a second compound having: PA0 (1) an aromatic group corresponding to the second aromatic group of the monomer (Ar.sup.2); PA0 (2) an "electron-deficient carbon group," as that term is previously defined, bonded to said aromatic group; and PA0 (3) a leaving group, as that term is previously defined, bonded to said aromatic group. PA0 (1) a first aromatic group (Ar.sup.1); PA0 (2) a first and a second azole ring fused to said first aromatic group; PA0 (3) a second aromatic group (Ar.sup.2) bonded to the 2-carbon of said first azole ring and a third aromatic group (Ar.sup.3) bonded to the 2-carbon of said second aromatic group; and PA0 (4) a first leaving group bonded to said second aromatic group and a second leaving group bonded to said third aromatic group, each in a position where it is activated by one of the azole rings. PA0 (1) an aromatic group corresponding to the second and third aromatic groups of the AA-monomer (Ar.sup.2 and Ar.sup.3); PA0 (2) an "electron-deficient carbon group" bonded to said aromatic group; and PA0 (3) a leaving groups as previously defined; PA0 (1) an aromatic group corresponding to the first aromatic group of the AA-monomer (Ar.sup.1); and PA0 (2) two o-amino-basic moieties bonded to said aromatic group. PA0 (1) an organic moiety (A) which is not electron-withdrawing and which is inert with respect to all reagents under reaction conditions; PA0 (2) two nucleophilic moieties, as that term is previously described, bonded to said divalent organic moiety; and PA0 (3) two counter-moieties, as that term is previously described, bonded to the nucleophilic ions. PA0 (1) a first aromatic group; PA0 (2) an azole ring fused to said first aromatic group; PA0 (3) a second aromatic group bonded to the 2-carbon of said azole ring; and PA0 (4) an oxygen, sulfur or nitrogen atom linked to said first aromatic group and bonded by a single bond to the second aromatic group of an adjacent mer unit. PA0 (1) a first aromatic group (Ar.sup.1); PA0 (2) a first and a second azole ring fused to said first aromatic group; PA0 (3) a second aromatic group (Ar.sup.2) bonded to the 2-carbon of said first azole ring and a third aromatic group (Ar.sup.3) bonded to the 2-carbon of said second aromatic group; PA0 (4) a first oxygen, sulfur or nitrogen atom bonded to said second aromatic group and a second oxygen, sulfur or nitrogen atom bonded to said first aromatic group; and PA0 (5) an organic moiety (A) bonded to said second oxygen, sulfur or nitrogen atom and to the first oxygen, sulfur or nitrogen atom of an adjacent unit.
Each mer unit preferably further comprises
Those mer units ordinarily comply with one of the following two formulae ##STR1## wherein: Ar.sup.1 is a first aromatic group as previously described;
PBZ polymers, their chemical structure, their properties and their synthesis are described in depth in numerous references such as 11 Ency. Poly, Sci & Eng., Polybenzothiazoles and Polybenzoxazoles, 601 (J. Wiley & Sons 1988); Wolfe et al., Liquid Crystalline Polymer Compositions and Process and Products, U.S. Pat. No. 4,703,103 (Oct. 27, 1987); Tsai et al., Method for Making Heterocyclic Block Copolymer, U.S. Pat. No. 4,578,432 (Mar. 25, 1986); Wolfe et al., Liquid Crystalline Poly(2,6-Benzothiazole) Compositions, Process and Products, U.S. Pat. No. 4,533,724 (Aug. 6, 1985); Wolfe, Liquid Crystalline Polymer Compositions, Process and Products, U.S. Pat. No. 4,533,693 (Aug. 6, 1985) and Wolfe et al., Liquid Crystalline Polymer Compositions and Process and Products, U.S. Pat. No. 4,533,692 (Aug. 6, 1985), which are incorporated herein by reference.
It is known in the art to synthesize PBZ polymers by the reaction of a first monomer comprising:
(b) a hydroxy, thio or amine group bonded to the first aromatic group in ortho position with respect to the primary amine group; PA1 (a) an azole ring; PA1 (b) an aromatic group bonded to the 2-carbon of said azole ring; and PA1 (c) a leaving group bonded to said aromatic group in a position such that it is activated by said azole ring, PA1 (a) an organic moiety which is not electron-withdrawing and which is inert with respect to all reagents under reaction conditions; PA1 (b) a nucleophilic moiety linked to said organic moiety, which nucleophilic moiety is a nitrogen atom having a hydrogen atom or inert organic substituent or an oxygen atom or a sulfur atom; and PA1 (c) a counter-moiety bonded to said nucleophilic moiety which can easily be removed therefrom. PA1 (a) azole-containing groups having: an azole ring bonded to said organic moiety, an aromatic group bonded to the 2-carbon of said azole ring, and a leaving group bonded to said aromatic ring in a position where it is activated by said azole ring; and
and a second monomer comprising:
The known syntheses for PBZ polymers ordinarily conform to one of the following two formulae: ##STR2## wherein: each Ar.sup.1 is a first aromatic group;
Those polymerizations have a number of drawbacks. First, polymerization is ordinarily carried out in a strong mineral acid such as polyphosphoric acid or a mixture of methanesulfonic acid and phosphorus pentoxide. Such acids are difficult to work with and must be washed from the resulting polymer by time-consuming rinsing over periods as long as 24 hours or longer. Second, monomers containing the o-amino-basic group are oxidatively unstable and must be stored as hydrogen halide salts, which are converted back to the basic monomer in the polymerization vessel by a time-consuming dehydrohalogenation step. Third, in the known syntheses the concentration of solids in the reaction mixture cannot ordinarily exceed 10 to 15 percent, so that large reaction vessels are necessary to synthesize small amounts of polymer.
What are needed are alternative processes for synthesizing PBZ polymers which do not rely upon the reaction of an o-amino-basic group with an electron-deficient carbon group to link monomers and which can avoid some or all of the drawbacks of the prior art processes.